Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02443933 2003-10-10
WO 02/084672 PCT/US02/10896
ELECTRICALLY CONDUCTIVE POLYMERIC MIXTURE,
METHOD OF MOLDING CONDUCTIVE ARTICLES USING SAME,
AND ELECTRICALLY CONDUCTIVE ARTICLES FORMED THEREFROM
BACKGROUND OF THE INVENTION
1. Field of the invention
The present invention relates to electrically conductive polymer compositions,
to
methods of use thereof, and to electrically conductive articles produced
therefrom. More
particularly, the present invention relates to a polymeric mixture containing
at least two
to conductive additives, to provide both surface conductivity and internal
conductivity, without
significantly affecting the physical properties of the polymer. The present
invention further
relates to methods of forming molded articles using the polymeric mixture, and
to electrically
conductive molded articles formed therefrom.
2. Description of the Background Art
15 Selected electrically conductive polymers are known and used in industrial
settings,
particularly in the manufacture of electronic component parts. Some examples
of electrically
conductive polymer compositions are illustrated in U.S. patent numbers:
5,256,335; 5,281,363;
5,378,403; 5,662,833; 5,958,303; 6,030,550; and 6,149,840.
U.S. patent no. 5,281,363 to Shacklette et al. is directed towards discrete
particles formed
20 of an electrically conductive polyaniline composition, which may be between
0.05 microns and
100 microns in size. In the particles of the '363 patent to Shacklette et al,
a first dopant
predominates at or near the surface of the particle, and a second dopant
predominates at or near
the core of the particle. The disclosure of Shacldette et al. is not
specifically directed to molded
articles, or to concentrations of electrically conductive additives in molded
articles. The
25 Shaklette patent offers surface and core conductivity within a particle;
however, this invention
CA 02443933 2003-10-10
WO 02/084672 PCT/US02/10896
utilizes salts and/or acids as surface additives which may provide a lower
rate of conductivity
than optimally possible, and which may also afford a limited range of thermal
stability.
LT.S. patent no. 5,662,833 to Laasko et al. discloses electrically conducting
thermoset
compositions, in which a thermoset matrix contains a polyaniline protonated
with a protonic acid
containing at least one hydroxyl group. In the Background section of Laasko,
conductive plastics
are generally categorized as either filled conductive plastics or
intrinsically conductive plastics.
While this reference goes on to list several conductive particles which are
usable as additives in
filled conductive plastics, it does not teach or suggest using a combination
of these additives to
provide both surface conductivity and core conductivity in a molded article.
1o While polymer compositions provide an electrically conductive medimn,
difficulty arises
in creating molded articles having both efficient surface conductivity and
electrostatic discharge
(ESD) capabilities. To utilize both electrical surface conductivity and ESD
efficiently,
conducting agents are necessary additives to the polymer's composition.
Selecting an additive
that performs a dual function of surface conductivity and ESD is difficult,
since eff dent surface
conductivity requires that the additive concentrate on or near the surface of
the polymer, and
efficient ESD requires that the additive concentrate around the core of the
polymer.
Adding a sufficient quantity of a single conducting agent to a polymer's
composition to
provide effective ESD, while also providing efficient surface conductivity,
often diminishes the
physical properties of the polymer. The problem of preserving the physical
properties of a
polymer while attempting to generate both eff cient surface conductivity and
ESD remains
elusive.
As a result, a need still exists in the art of electrically conductive polymer
compositions
for a material or mixture that pxovides both surface conductivity and ESD
performance. In
2
CA 02443933 2003-10-10
WO 02/084672 PCT/US02/10896
particular, there is a need for a material that operates to conduct electrical
current on the surface
area and provides electrostatic discharge without significantly diminishing
the physical
properties of the polymer composition.
One example of a possible application of a conductive polymeric material is in
a plastic
fuel filter housing. Contemporary fuel filters are formed using plastic
housings in many instances
today. Unfortunately, there is some risk that a fuel filter may build up
static electricity within the
plastic housing thereof.
In the event that a plastic fuel filter housing, having fuel stored therein,
was exposed to a
spark caused by sudden electrostatic discharge, the consequences could be
hazardous if such a
to spark were to ignite fuel in, on or near the fuel filter. Accordingly, it
would be desirable to form
a plastic housing for a fuel filter in which the housing could be electrically
conductive, and could
be connected to ground in order to avoid the buildup of static electricity
therein, and consequent
sudden electrostatic discharge.
SUMMARY OF THE INVENTION
is The present invention has been developed to overcome the foregoing
limitations and
disadvantages of known electrically conductive polymer compositions, and to
generally fulfil a
need in the art for a dual conductive polymer which provides both surface area
electrical
conductivity and electrostatic discharge, while maintaining the physical
properties of the
polymer composition.
2o The polymeric mixture according to the present invention conducts
electricity primarily
through the inclusion of electrically conductive additives, rather than by
using inherently
conductive polymers. In practicing the invention, two different additives are
used, a first
additive to provide surface conductivity and a second additive to provide core
conductivity.
CA 02443933 2003-10-10
WO 02/084672 PCT/US02/10896
An electronically conductive polymer composition, in accordance with the
present
invention, includes
a) a polymeric material;
b) a first electrically conductive additive selected from the group consisting
of metallic
fibers and metallic particles; and
c) a second electrically conductive additive selected from the group
consisting of carbon
fibers and carbon particles.
Such an electrically conductive polymer composition is advantageous because it
provides
both surface conductivity and electrostatic discharge capability, without
diminishing the physical
1 o properties of the polymer composition.
Preferably, the polymeric material is a thermoplastic selected from the group
consisting
of polyamides, polyimides, polyesters, polyolefins, polysulfones,
fluoropolymers, and mixtures
thereof. Particularly preferred polymeric materials are acetal and nylon 12.
Preferred additives are carbon particles and stainless steel fibers, and most
preferably, the
15 mixture contains both carbon powder and stainless steel fibers together.
The present invention also relates to a method of making an electrically
conductive molded article, comprising the steps of:
a) injecting a polymer mixture into a mold cavity having formed within a
hollow mold,
said mold cavity having an outer periphery;
2o said polymer mixture comprising:
a polymeric material;
a first electrically conductive additive selected from the group consisting
of metallic fibers and metallic particles; and
4
CA 02443933 2003-10-10
WO 02/084672 PCT/US02/10896
a second electrically conductive additive selected from the group
consisting of carbon fibers and carbon particles;
whereby the first electrically conductive additive migrates away from the
outer periphery of the mold cavity, and the second electrically conductive
additive
migrates toward the outer periphery of the mold cavity;
b) curing the polymer in the hollow mold to form a molded article; and
c) ejecting the molded article from the mold.
The present invention also relates to an electrically conductive molded
article which is a
product of the above-described process. In particular, one example of a useful
molded article in
to accordance with the invention is a fuel filter housing.
Accordingly, it,is an object of the present invention to provide a mixture
which is suitable
for forming electrically conductive molded articles able to conduct electric
current within the
surface area thereof, and consistently performing electrostatic discharge
while maintaining the
structural integrity of the polymer composition.
15 For a more complete understanding of the present invention, the reader is
referred to the
following detailed description section, which should be read in conjunction
with the
accompanying drawings. Throughout the following detailed description and in
the drawings, like
numbers refer to like parts.
2o BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic diagram showing a sequence of steps in forming a
molded article
according to a method of the present invention;
Figure 2 is a cross-sectional view of a fuel filter; and
CA 02443933 2003-10-10
WO 02/084672 PCT/US02/10896
Figure 3 is a simplified cross section, partially cut away, of part of a side
wall of the fuel
filter housing of Figure 2, taken along the line 3-3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In a first embodiment thereof, the present invention provides a composition
which
is a mixture of a polymer and at least two different electrically conductive
additives. A mixture
in accordance with the present invention, generally, includes:
a) a pulverized polymeric material;
b) a first electrically conductive additive selected from the group consisting
of metallic
fibers and metallic particles; and
1 o c) a second electrically conductive additive selected from the group
consisting of carbon
fibers and carbon particles.
Preferably, the pulverized polymeric material is a thermoplastic. Suitable
thermoplastic
materials usable in the practice of the present invention include polyamides,
polyimides,
polyesters, polyolefins, polysulfones, fluoropolymers, and mixtures thereof
15 One particularly preferred thermoplastic is polyacetal resin polymer, also
called
polyoxymethylene, which is a product of the polymerization of a formaldehyde-
containing
starting material. This material is often referred to by the abbreviated name
"acetal" or "POM".
One suitable type of acetal resin polymer, which may be used in the practice
of the present
invention, is that sold commercially by DuPont under the trademark "DELRIN".
Another
2o suitable thermoplastic is Nylon 12.
Most preferably, the mixture according to the invention includes both carbon
particles
and stainless steel fibers.
The present invention also relates to a method of making an electrically
CA 02443933 2003-10-10
WO 02/084672 PCT/US02/10896
conductive molded article, comprising the steps of:
a) injecting a polymer mixture into a mold cavity having formed within a
hollow mold,
said mold cavity having an outer periphery;
said polymer mixture comprising:
a polymeric material;
a f rst electrically conductive additive selected from the group consisting
of metallic fibers and metallic particles; and
a second electrically conductive additive selected from the group
consisting of carbon fibers and carbon particles;
whereby the first electrically conductive additive migrates away from the
outer periphery of the mold cavity, and the second electrically conductive
additive
migrates toward the outer periphery of the mold cavity;
b) curing the polymer in the hollow mold to form a molded article; and
c) ejecting the molded article from the mold.
The above-described method may also include preparatory steps of mixing the
additives
into the pulverized polymer, and melting the polymer, where a thermoplastic is
used, to form the
flowable mixture which is then injected into the mold.
Referring now to Figure 1, a series of steps in one particularly preferred
method
according to the invention is shown schematically.
2o An initial step of mixing the additives into the dry pulverized polymer is
shown at 20. As
previously noted, the most preferred additives are carbon particles and
stainless steel fibers.
The next step, shown at 22 in Figure 1, is melting the thermoplastic polymer
to form a
flowable mixture.
CA 02443933 2003-10-10
WO 02/084672 PCT/US02/10896
Then, in an injection step 24, the flowable mixture is injected into a mold
cavity using
conventional injection molding equipment. During and immediately subsequent to
the injection
step 24, the heated mixture exhibits a natural tendency for the carbon
particles to migrate
towards the outer periphery of the mold, while the steel fibers remain at or
near the core.
After the injection step, the mold is cooled in a cooling step 26, allowing
the polymer to
set and form a molded article 10 (Figure 2). In the example shown in Figure 2,
the molded article
is part of a housing for a fuel filter 12.
The finished article is then ejected from the mold in an ejection step 28.
The present invention also relates to an electrically conductive molded
article which is a
1o product of the above-described process. In particular, one example of a
useful molded article 10
in accordance with the invention is a fuel filter housing.
Referring now to Figure 3, a portion of a side wall 14 of the article 10 is
shown. In the
cross-sectional view of Figure 3, it can be clearly seen that the carbon
particles 16 tend to
concentrate at or near the surface 15 of the article 10, which gives the
article good surface
15 conductivity. In contrast, the stainless steel fibers 18 tend to remain at
or near the center or core
17 of the article 10, which advantageously also provides internal conductivity
which promotes
electrostatic discharge (ESD).
Although the present invention has been described herein with respect to a
preferred
embodiment thereof, the foregoing description is intended to be illustrative,
and not restrictive.
2o Those skilled in the art will realize that many modifications of the
preferred embodiment could
be made which would be operable. All such modifications which are within the
scope of the
claims are intended to be within the scope and spirit of the present
invention.
